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Supporting information on
Conversion reactions for sodium-ion batteries
Franziska Klein, Birte Jache, Amrtha Bhide, Philipp Adelhelm*
Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 58, 35392
Giessen
Corresponding author: Dr. Philipp Adelhelm ([email protected])
Figure S1
a) Differences in lattice enthalpies latticeH°(Li-Na) and differences in cell potentials E°(Li-Na) for lithium and
sodium based compounds (LiI/NaI, LiBr/NaBr, LiCl/NaCl, LiH/NaH, LiF/NaF, Li2S/Na2S, and Li2O/Na2O).
Values for the lattice enthalpies were calculated by the Born-Haber cycle. Cell potentials have been calculated
by using the thermodynamic database from HSC Chemistry 7.0.
As can be seen, a linear relationship between values for latticeH°(Li-Na) and E°(Li-Na) exists (y=0.0103x-0.7655).
b) X-axis replaced by the differences in lattice energies latticeU(Li-Na). Source for lattice energies U: CRC
Handbook of Chemistry and Physics 84th
edition, Chapter 12, page 22. Values for lattice enthalpies can be
directly calculated from the lattice energies, however, the differences are negligible (< 0.5 % for the compounds
discussed here). The linear behavior is in line with what is shown in a). Interestingly, Li2S/Na2S deviates from
the linear correlation. This behavior cannot be explained so far but might be due to incorrect thermodynamic
data for the reported lattice energies. Estimating the lattice energy by the Kapustinskii equation (c) shows no
significant deviation from the linear relationship for sulfides.
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Figure S2 Contribution of the conductive additive (15wt% Super PLi and 10% SFG-44 graphite) to the overall
capacity obtained for the CuO electrode.
a: Capacity of an electrode without CuO but the same weight ratio of Super PLi and SFG-44 as the one that is
used for the conversion electrodes. The specific capacity has been normalized to the content that is present in the
conversion electrode, i.e. 25wt%.
b: Graphical illustration of the amount of capacity that is due to the carbon additive. Upon discharge, the
contribution is around 10 %. Upon charge and subsequent cycling, the contribution is below 10 %.
Figure S3 X-ray diffraction pattern of CuCl2 electrodes before (reference) and after the first discharge and
charge.
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Figure S4 Cycling stability of conversion reactions of CuCl2 with lithium and sodium.
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Table S1: Additional thermodynamic data for lithium and sodium based conversion reactions. The
theoretical capacity q [Ah.kg-1
] is calculated by qth=(z∙F)/(3.6∙M) with z being the number of
transferred electrons, F as Faraday constant and M as molar mass of the compound before conversion.
The theoretical energy density wth is calculated by wth=E°∙q.
The general conversion reaction is
M X ( ) A M A X
A= Li or Na
a b cb c a b
Values for ΔE°(LiNa) within a class of compounds (hydrides, oxides, sulfides, fluorides, chlorides,
bromides, iodides) are always the same due to the following reactions.
Hydrides
1Li NaH LiH Na 34.82 kJ.mol ; °= 0.36 VrG E
Nitrides
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE° / V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
TiN 3 1299 n/a 180.56 n/a − 0.62 n/a n/a − 606
VN 3 1238 n/a 62.47 n/a − 0.22 n/a n/a − 202
CrN 3 1218 n/a − 35.8 n/a 0.12 n/a n/a 115
Mn4N 3 344 n/a − 24.34 n/a 0.08 n/a n/a 27
Mn3N2 6 834 n/a − 110.75 n/a 0.19 n/a n/a 131
Fe4N 3 339 n/a − 132.33 n/a 0.46 n/a n/a 142
Co3N 3 421 n/a − 163.00 n/a 0.56 n/a n/a 214
Ni3N 3 423 n/a − 155.47 n/a 0.54 n/a n/a 205
Cu3N 3 393 n/a n/a n/a n/a n/a n/a n/a
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE °/ V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
TiH2 2 1074 38.03 − 31.62 − 0.20 0.16 0.36 − 110 138
CuH 1 415 − 88.68 − 123.9 0.92 1.28 0.36 281 480
MgH2 2 2036 − 30.72 − 100.37 0.16 0.52 0.36 118 695
CaH2 2 1273 + 75.43 + 5.78 − 0.39 − 0.03 0.36 − 238 − 29
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Phosphides
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE °/ V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
CrP 3 969 − 67.41 n/a 0.23 n/a n/a 123 n/a
MnP 3 936 − 62.87 n/a 0.22 n/a n/a 113 n/a
FeP 3 926 − 91.87 n/a 0.32 n/a n/a 164 n/a
FeP2 6 1365 − 228.93 n/a 0.40 n/a n/a 249 n/a
Fe3P 3 405 − 28.87 n/a 0.10 n/a n/a 0 n/a
Fe2P 3 564 − 49.56 n/a 0.17 n/a n/a 65 n/a
CoP 3 894 −40.59 n/a 0.14 n/a n/a 71 n/a
CoP3 3 1589 − 296.36 n/a 0.34 n/a n/a 229 n/a
NiP2 6 1333 − 252.88 n/a 0.44 n/a n/a 272 n/a
NiP3 9 1591 − 418.95 n/a 0.48 n/a n/a 325 n/a
Ni2P 3 542 − 14.49 n/a 0.05 n/a n/a 19 n/a
CuP2 6 1281 − 258.76 n/a 0.45 n/a n/a 273 n/a
Cu3P 3 363 − 14.99 n/a 0.05 n/a n/a 14 n/a
Note: The standard free enthalpy of formation of Na3P is an estimate taken from ref JM Sangster,
Journal of Phase Equilibria and Diffusion, Vol. 31, No 1, 2010, pages 62-67
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Oxides
12 22 Li Na O Li O 2 Na 184.85 kJ.mol ; °= 0.96 VrG E
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE° / V
ΔE°(LiNa)
wth / Wh kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
TiO2 4 1342 137.00 − 232.88 − 0.35 0.60 0.96 − 221 601
VO2 4 1293 − 93.37 − 463.07 0.24 1.20 0.96 148 1162
CrO2 4 1276 − 223.24 − 592.93 0.58 1.54 0.96 352 1474
MnO 2 756 − 13.47 − 198.31 0.07 1.03 0.96 32 649
MnO2 4 1233 − 287.48 − 657.18 0.74 1.70 0.96 446 1592
Mn2O3 6 1019 − 247.93 −802.47 0.43 1.39 0.96 233 1117
FeO 2 746 − 125.72 − 310.56 0.65 1.61 0.96 296 1006
Fe2O3 6 1007 − 384.66 − 939.20 0.66 1.62 0.96 359 1296
CoO 2 715 − 162.10 − 346.95 0.84 1.80 0.96 372 1085
Co3O4 8 891 − 710.30 − 1449.68 0.92 1.88 0.96 465 1359
NiO 2 718 − 164.72 − 349.56 0.85 1.81 0.96 379 1096
CuO 2 674 − 246.71 − 431.55 1.28 2.24 0.96 546 1283
Cu2O 2 375 − 230.44 − 415.29 1.19 2.15 0.96 338 735
ZnO 2 659 − 58.15 − 243.00 0.30 1.26 0.96 129 724
RuO2 4 806 − 499.94 − 869.64 1.30 2.25 0.96 617 1502
Al2O3 6 1577 453.51 − 101.17 − 0.78 0.17 0.96 − 525 196
Ga2O3 6 858 − 130.51 − 685.05 0.23 1.18 0.96 111 831
In2O3 6 579 − 298.17 − 852.71 0.52 1.47 0.96 199 742
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Sulfides
12 22 Li Na S Li S 2 Na 74.80 kJ.mol ; °= 0.39 VrG E
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE° / V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
TiS2 4 957 − 320.46 − 470.06 0.83 1.22 0.39 436 934
MnS 2 616 − 138.57 − 213.37 0.72 1.11 0.39 289 588
MnS2 4 900 − 488.78 − 638.38 1.27 1.65 0.39 643 1208
FeS 2 610 − 257.48 − 332.28 1.33 1.72 0.39 534 907
FeS2 4 894 − 548.77 − 698.38 1.42 1.81 0.39 719 1313
Co3S4 8 703 − 1095.73 − 1394.94 1.42 1.81 0.39 622 1075
CoS 2 589 − 261.00 − 335.80 1.35 1.74 0.39 529 889
NiS 2 591 − 266.41 − 341.21 1.38 1.77 0.39 541 906
Ni3S2 4 446 − 505.20 − 654.80 1.31 1.70 0.39 422 679
CuS 2 561 − 304.02 − 378.82 1.58 1.96 0.39 596 961
Cu2S 2 337 − 269.15 − 343.95 1.39 1.78 0.39 364 552
ZnS 2 550 − 159.25 − 234.06 0.83 1.21 0.39 308 584
Al2S3 6 1071 − 435.51 − 659.92 0.75 1.14 0.39 420 956
Ga2S3 6 682 − 567.56 − 791.97 0.98 1.37 0.39 422 793
In2S3 6 494 − 731.95 − 956.36 1.26 1.65 0.39 438 723
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Fluorides
1Li NaF LiF Na 42.31 kJ.mol ; °= 0.44 VrG E
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE° / V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
ScF3 3 789 − 99.18 − 226.10 0.34 0.78 0.44 161 512
TiF3 3 767 − 277.17 − 404.09 0.96 1.40 0.44 443 893
VF2 2 603 − 146.77 − 231.38 0.76 1.20 0.44 302 625
VF3 3 745 − 412.54 − 539.46 1.43 1.86 0.44 648 1164
CrF3 3 738 − 548.75 − 675.67 1.89 2.33 0.44 856 1446
MnF2 2 577 − 280.24 − 364.86 1.45 1.89 0.44 560 949
FeF2 2 571 − 424.06 − 508.68 2.20 2.64 0.44 842 1312
FeF3 3 712 − 714.06 − 840.98 2.47 2.91 0.44 1091 1748
CoF2 2 553 − 464.67 − 549.28 2.41 2.85 0.44 903 1377
NiF2 2 554 − 482.81 − 567.42 2.50 2.94 0.44 940 1425
CuF2 2 528 − 597.13 − 681.74 3.09 3.53 0.44 1124 1641
ZnF2 2 518 − 379.19 − 463.81 1.96 2.40 0.44 705 1099
Chlorides
1Li NaCl LiCl Na 0.07 kJ.mol ; °= - 0.0007 VrG E
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE° / V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
ScCl3 3 531 − 299.32 − 299.12 1.03 1.03 0.00 377 483
TiCl4 4 565 − 801.12 − 800.86 2.08 2.08 0.00 1018 1023
VCl2 2 440 − 362.64 − 362.51 1.88 1.88 0.00 600 742
VCl3 3 511 − 640.93 − 640.73 2.21 2.21 0.00 787 999
MnCl2 2 426 − 327.73 − 327.59 1.70 1.70 0.00 530 651
FeCl2 2 423 − 466.26 − 466.16 2.42 2.42 0.00 750 921
FeCl3 3 496 − 818.22 − 818.02 2.83 2.83 0.00 983 1242
CoCl2 2 413 − 498.56 − 498.43 2.58 2.58 0.00 788 963
NiCl2 2 414 − 509.10 − 508.97 2.64 2.64 0.00 805 985
CuCl 1 271 − 264.52 − 264.45 2.74 2.74 0.00 602 693
CuCl2 2 399 − 593.22 − 593.09 3.07 3.07 0.00 913 1111
ZnCl2 2 393 − 397.83 − 397.70 2.06 2.06 0.00 606 736
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Bromides
1Li NaBr LiBr Na 7.24 kJ.mol ; °= - 0.08 VrG E
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE° / V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
ScBr3 3 282 − 329.81 − 308.10 1.14 1.06 − 0.08 259 280
TiBr4 4 292 − 805.66 − 776.71 2.09 2.01 − 0.08 487 546
VBr2 2 277 − 350.34 − 335.86 1.82 1.74 − 0.08 379 415
VBr3 3 291 − 633.87 − 612.15 2.19 2.11 − 0.08 447 546
CrBr3 3 276 − 674.75 − 653.04 2.33 2.26 − 0.08 520 580
MnBr2 2 250 − 327.08 − 312.6 1.69 1.62 − 0.08 348 380
FeBr2 2 249 − 460.85 − 446.37 2.39 2.31 − 0.08 489 540
FeBr3 3 272 − 802.39 − 780.67 2.77 2.70 − 0.08 611 685
CoBr2 2 245 − 496.87 − 482.39 2.57 2.50 − 0.08 521 576
NiBr2 2 245 − 504.07 −489.59 2.61 2.54 − 0.08 529 585
CuBr 1 187 − 248.01 −240.76 2.57 2.50 − 0.08 414 445
CuBr2 2 240 − 576.19 − 561.71 2.99 2.91 − 0.08 594 658
ZnBr2 2 238 − 385.69 − 371.21 2.00 1.92 − 0.08 395 431
Iodides
1Li NaI LiI Na 14.33 kJ.mol ; °= - 0.15 VrG E
Compound z qth / Ah.kg-1 ΔrG / kJ.mol-1 ΔE° / V
ΔE°(LiNa)
wth / Wh.kg-1
vs. Na/Na+ vs. Li/Li+ vs. Na/Na+ vs. Li/Li+ Na Li
ScI3 3 189 − 291.96 − 248.92 1.01 0.86 − 0.15 164 156
TiI4 4 193 − 767.74 − 710.44 1.99 1.84 − 0.15 329 338
VI2 2 176 − 305.18 − 276.53 1.58 1.43 − 0.15 242 241
VI3 3 186 − 573.51 − 530.54 1.98 1.83 − 0.15 318 326
MnI2 2 174 − 325.84 − 297.19 1.69 1.54 − 0.15 255 256
FeI2 2 173 − 457.44 − 428.79 2.37 2.22 − 0.15 357 368
FeI3 3 184 − 747.02 − 704.04 2.58 2.43 − 0.15 410 428
CoI2 2 171 − 474.05 − 445.40 2.46 2.31 − 0.15 367 379
NiI2 2 172 − 474.95 − 446.30 2.46 2-31 − 0.15 368 380
CuI 1 140 − 215.36 − 201.03 2.23 2.08 − 0.15 280 283
ZnI2 2 168 − 358.91 − 330.26 1.86 1.71 − 0.15 273 275
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Table S2: Volume expansion for a series of lithium (A = Li) and sodium (A = Na) based conversion
reactions.
M X + (b c) A M + A Xa b ca b
volume expansion (%) 100 100c
a b
V b A X V a M
V M X
Hydrides
Compound Volume expansion / %
Na Li
TiH2 239.3 125.5
MgH2 167.2 83.8
CaH2 144.3 82.7
Nitrides
Compound Volume expansion / %
Na Li
TiN n/a 220.9
VN n/a 239.5
CrN n/a 209.8
Mn4N n/a n/a
Mn3N2 n/a n/a
Fe4N n/a 54.6
Co3N n/a n/a
Ni3N n/a n/a
Cu3N n/a n/a
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Phosphides
Compound Volume expansion / %
Na Li
CrP 327.9 217.7
MnP 314.3 207.8
FeP n/a n/a
FeP2 429.2 284.6
Fe3P 167.4 110.8
Fe2P 241.5 162.1
CoP 374.7 251.4
Co3P n/a n/a
NiP2 392.3 257.3
NiP3 n/a n/a
Ni2P 248.9 166.6
CuP2 308.2 196.7
Cu3P 130.9 82.0
Oxides
Compound Volume expansion / %
Na Li
TiO2 245.4 113.5
VO2 230.4 100.0
CrO2 260.0 114.9
MnO 162.7 68.3
MnO2 262.3 116.7
Mn2O3 176 69
FeO 187.4 83.3
Fe2O3 215.4 92.8
CoO 192.3 85.0
Co3O4 227.8 101.3
NiO 205.0 92.9
CuO 172.8 74.0
Cu2O 74.0 21.7
ZnO 151.2 65.3
RuO2 190.0 100.5
Al2O3 296.2 150.9
Ga2O3 262.5 134.1
In2O3 193.0 96.4
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Sulfides
Compound Volume expansion / %
Na Li
TiS2 185.0 100.5
MnS 127.3 62.8
MnS2 166.1 84.5
FeS 165.0 89.4
FeS2 281.6 164.2
Co3S4 199.8 110.3
CoS 191.7 107.6
NiS 193.2 108.6
Ni3S2 153.8 85.3
CuS 144.7 74.8
Cu2S 97.9 48.5
ZnS 109.1 51.8
Al2S3 96.6 40.0
Ga2S3 132.0 66.7
In2S3 115.2 58.7
Fluorides
Compound Volume expansion / %
Na Li
ScF3 55.1 14.5
TiF3 58.9 14.1
VF2 72.1 25.4
VF3 67.8 18.6
CrF3 83.2 28.2
MnF2 61.0 16.0
FeF2 62.6 16.8
FeF3 79.8 25.6
CoF2 69.6 21.2
NiF2 78.9 27.8
CuF2 55.4 11.6
ZnF2 88.5 38.1
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Chlorides
Compound Volume expansion / %
Na Li
ScCl3 51.7 20.9
TiCl4 n/a n/a
VCl2 65.8 31.3
VCl3 70.8 33.6
MnCl2 45.2 14.5
FeCl2 52.3 19.9
FeCl3 57.4 22.6
CoCl2 56.7 23.2
NiCl2 65.9 30.4
CuCl2 53.8 21.1
CuCl 42.5 15.4
ZnCl2 34.8 7.0
Bromides
Compound Volume expansion / %
Na Li
ScBr3 53.2 24.1
TiBr4 27.6 1.7
VBr2 58.2 27.5
VBr3 44.4 15.3
CrBr3 66.2 32.3
MnBr2 46.3 17.5
FeBr2 53.4 23.1
FeBr3 57.5 25.3
CoBr2 59.1 27.5
NiBr2 65.3 32.4
CuBr 36.1 11.7
CuBr2 52.4 22.2
ZnBr2 46.7 18.5
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Iodides
Compound Volume expansion / %
Na Li
ScI3 52.3 25.8
TiI4 54.0 27.4
VI2 61.5 32.0
VI3 58.6 29.7
CrI3 48.7 22.0
MnI2 45.8 19.7
FeI2 52.4 20.0
CoI2 60.8 31.8
NiI2 65.1 35.3
CuI 43.0 19.3
ZnI2 35.1 11.4
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